The invention provides a process for hydrogenating aromatic polymers, which is characterised in that Group VIII metals are present together with a support of silicon dioxide or aluminium oxide or mixtures thereof. The catalysts have a specific pore size distribution. This enables the aromatic units of aromatic polymers to be hydrogenated completely, without a significant decrease in molecular weight.
Hydrogenation of aromatic polymers is already known. DE-AS 1 131 885 describes the hydrogenation of polystyrene in the presence of catalysts and solvent. Aliphatic and cycloaliphatic hydrocarbons, ethers, alcohols and aromatic hydrocarbons are mentioned as the solvents. A mixture of cyclohexane and tetrahydrofuran is named as preferable. Silicon dioxide and aluminium oxide catalyst supports are mentioned in a general manner, their physico-chemical structure not, however, being described.
EP-A-322 731 describes the preparation of predominantly syndiotactic polymers based on vinyl cyclohexane, wherein a styrene-based polymer is hydrogenated in the presence of hydrogenation catalysts and solvents. Cycloaliphatic and aromatic hydrocarbons, but not ethers, are mentioned as the solvents.
DE 196 24835 (=EP-A 814 098) for the hydrogenation of polymers with ruthenium or palladium catalysts, in which the active metal is applied to a porous support, describes the hydrogenation of olefinic double bonds of polymers.
The hydrogenation level of aromatic regions is less than 25% and is generally within the range 0 to approximately 7%. The choice of solvents is not critical here.
It is furthermore known (WO 96/34896=U.S. Pat. No. 5,612,422) that in the hydrogenation of aromatic polymers small pore diameters (200-500 xc3x85) and large surface areas (100-500 m2/g) of silicon dioxide-supported catalysts result in incomplete hydrogenation and in degradation of the polymer chain. The use of specific silicon dioxide-supported hydrogenation catalysts (WO 96/34896) permits virtually complete hydrogenation with an approximately 20% decrease in molecular weight. The silicon dioxide of the named catalysts has a specific pore size distribution which is characterised in that 98% of the pore volume is defined by pores of a diameter greater than 600 xc3x85. The named catalysts have surface areas of between 14 and 17 m2/g and average pore diameters of from 3800 to 3900 xc3x85. The hydrogenation levels achieved on dilute polystyrene solutions in cyclohexane at a concentration of between 1% and 8% maximum are greater than 98% and less than 100%.
The examples described in the named specifications show a decrease in the absolute molecular weight of the hydrogenated polystyrene when polymer concentrations are less than 2%. Decreased molecular weight generally leads to a deterioration in the mechanical properties of a hydrogenated polystyrene.
The Comparative Example according to WO 96/34896 of a commercially available catalyst 5% Rh/Al2O3 (Engelhard Corp., Beachwood, Ohio, USA) yields a 7% hydrogenation level and shows that the activity of the aluminium oxide support is lower than that of the silicon dioxide-supported catalyst.
It has surprisingly now been found that aromatic polymers are hydrogenated completely and with no significant decrease in molecular weight when specific catalysts are used which comprise Group VIII metals together with a support of silicon dioxide, aluminium oxide or a mixture thereof, which are defined in that at least 10%, preferably 15%, of the pore volume is defined by pores of a diameter less than 600 xc3x85, and they have an average pore diameter of 900 xc3x85 maximum, a BET surface area of at least 40 m2/g and a defined pore size distribution.
The invention provides a process for hydrogenating aromatic polymers in the presence of catalysts, wherein the catalyst is a metal or a mixture of metals from Group VIII of the Periodic Table together with a support of silicon dioxide, aluminium oxide or a mixture thereof, and the catalyst pore volume defined by pores of diameters between 100 and 1000 xc3x85, measured by mercury porosimetry, is generally from 100 to 15%, preferably from 90 to 20% and most particularly preferably 80 to 25%, in particular 70 to 25%, in relation to the total pore volume, measured by mercury porosimetry.
The average pore diameter, determined by mercury porosimetry, is 900 xc3x85 maximum.
The mercury method is, however, sufficiently accurate only for pores larger than 60 xc3x85. Pore diameters of less than 600 xc3x85 are therefore determined by nitrogen sorption according to Barret, Joyner, Halenda (DIN 66 134).
The catalysts therefore additionally have a 100 to 10%, preferably 80 to 10%, in particular 70 to 15% pore volume, measured by nitrogen sorption, which is defined by pores of diameters of less than 600 xc3x85. The pore volume, measured by nitrogen sorption, relates to the total pore volume, measured by mercury porosimetry.
The average pore diameter and the pore size distribution are determined by mercury porosimetry in accordance with DIN 66 133.
The average pore diameter is generally from 10 to 1000 xc3x85, preferably 50 to 950 xc3x85, most particularly preferably 60 to 900 xc3x85.
Methods for characterising hydrogenation catalysts are described, for example, in WO 96/34896 (=U.S. Pat. No. 5,612,422) and Applied Heterogeneous Catalysis, Institut Francais du Pxc3xa9trole Publication, pp. 189-237 (1987).
The catalysts consist of Group VIII metals which are present together with a support of silicon dioxide or aluminium oxide or mixtures thereof.
The surface area of the catalyst is determined in accordance with BET (Brunauer, Emmett and Teller) processes by nitrogen adsorption, in accordance with DIN 66 131 and DIN 66 132.
The specific nitrogen surface areas (BET) are generally from 40 to 800 m2/g, preferably 50 to 600 m2/g.
Group VIII metals, preferably nickel, platinum, ruthenium, rhodium, palladium, in particular platinum, palladium and nickel, are generally used.
The metal content, in relation to the total weight of the catalyst, is generally from 0.01 to 80%, preferably 0.05 to 70%.
The 50% value of the cumulative distribution of particle size is generally from 0.1 xcexcm to 200 xcexcm, preferably 1 xcexcm to 100 xcexcm, most particularly preferably 3 xcexcm to 80 xcexcm, in the batch process.
Conventional solvents for hydrogenation reactions are aliphatic or cycloaliphatic hydrocarbons, aliphatic or cycloaliphatic saturated ethers or mixtures thereof, for example, cyclohexane, methylcyclopentane, methylcyclohexane, ethylcyclohexane, cyclooctanes, cycloheptane, dodecane, dioxane, diethylene glycol dimethyl ether, tetrahydrofuran, isopentane, decahydronaphthalene.
If aliphatic or cycloaliphatic hydrocarbons are used as solvents, they preferably contain water in a quantity of generally from 0.1 ppm to 500 ppm, preferably 0.5 ppm to 200 ppm, most particularly preferably 1 ppm to 150 ppm, in relation to the total solvent.
The process according to the invention generally leads to practically complete hydrogenation of the aromatic units. The hydrogenation level is generally xe2x89xa780%, preferably xe2x89xa790%, most particularly preferably xe2x89xa799% to 100%. The hydrogenation level can be determined by NMR or UV spectroscopy, for example. The process according to the invention results most particularly preferably in hydrogenated aromatic polymers, in particular polyvinyl cyclohexane, wherein the quantity of diads having syndiotactic configuration is greater than 50.1% and less than 74%, in particular from 52 to 70%.
Aromatic polymers which are selected, for example, from among polystyrene optionally substituted in the phenyl ring or on the vinyl group, or copolymers thereof with monomers selected from the group comprising olefins, (meth)acrylates or mixtures thereof, are used as starting materials. Further suitable polymers are aromatic polyethers, in particular polyphenylene oxide, aromatic polycarbonates, aromatic polyesters, aromatic polyamides, polyphenylenes, polyxylylenes, polyphenylene vinylenes, polyphenylene ethylenes, polyphenylene sulfides, polyaryl ether ketones, aromatic polysulfones, aromatic polyether sulfones, aromatic polyimides and mixtures thereof, copolymers, optionally copolymers with aliphatic compounds.
C1-C4-alkyl, such as methyl, ethyl, C1-C4-alkoxy, such as methoxy, ethoxy, condensed aromatics bonded with the phenyl ring by way of either one or two carbon atoms are considered with phenyl, biphenyl, naphthyl, as substituents in the phenyl ring.
C1-C4-alkyl, such as methyl, ethyl, n-propyl or iso-propyl, in particular methyl in the xcex1-position, are considered as substituents on the vinyl group.
Olefinic comonomers which are considered are ethylene, propylene, isoprene, isobutylene, butadiene, cyclohexadiene, cyclohexene, cyclopentadiene, optionally substituted norbornenes, optionally substituted dicyclopentadienes, optionally substituted tetracyclododecenes, optionally substituted dihydrocyclopentadienes,
C1-C8-, preferably C1-C4-alkylesters of (meth)acrylic acid, preferably methyl and ethylesters,
C1-C8-, preferably C1-C4-alkylethers of vinyl alcohol, preferably methyl and ethylethers,
C1-C8-, preferably C1-C4-alkylesters of vinyl alcohol, preferably vinyl acetate, derivatives of maleic acid, preferably maleic anhydride, derivatives of acrylonitrile, preferably acrylonitrile and methacrylonitrile.
Preferred polymers are polystyrene, polymethylstyrene, copolymers of styrene and at least one further monomer, selected from the group comprising xcex1-methylstyrene, butadiene, isoprene, acrylonitrile, methylacrylate, methylmethacrylate, maleic anhydride and olefins such as, for example, ethylene and propylene. Copolymers of acrylonitrile, butadiene and styrene, copolymers of acrylic ester, styrene and acrylonitrile, copolymers of styrene and xcex1-methylstyrene and copolymers of propylene, diene and styrene, for example, are considered.
The aromatic polymers generally have weight average molecular weights Mw of from 1000 to 10000000, preferably 60000 to 1000000, particularly preferably 70000 to 600000, in particular 100000 to 480000, determined by light scattering.
Both linear-chain structures and structures having branching points from co-units (for example graft copolymers) are possible for the polymers. The branching centres contain, for example, star-shaped polymers or other geometric forms of the primary, secondary, tertiary, optionally quaternary polymer structure.
The copolymers may be present as random, alternating and also block copolymers.
Block copolymers include di-blocks, tri-blocks, multi-blocks and star-shaped block copolymers.
The starting polymers are generally known (for example WO 94/21 694).
The quantity of catalyst to be used is described in WO 96/34896, for example.
The quantity of catalyst to be used depends on the process to be carried out; it may be operated as a continuous, semi-continuous or batch process.
The reaction time is substantially shorter in the continuous system; it is influenced by the dimensions of the reaction vessel. In the continuous operating method, both the trickle-bed system and the liquid phase system, both having catalysts arranged in fixed manner, are as feasible as a system having suspended and, for example, circulated catalyst. The catalysts arranged in fixed manner may be present in tablet form or as extrudates.
In the batch process the polymer concentrations, in relation to the total weight of solvent and polymer, are generally from 80 to 1, preferably 50 to 10, in particular 40 to 15 wt. %.
The reaction is generally carried out at temperatures of between 0 and 500xc2x0 C., preferably between 20 and 250xc2x0 C., in particular between 60 and 200xc2x0 C.
The reaction is generally carried out at pressures of from 1 bar to 1000 bar, preferably 20 to 300 bar, in particular 40 to 200 bar.
The catalysts may be used both reduced and also unreduced in the relevant reaction. For an industrial process use of the unreduced catalyst is more favourable by far, omitting an additional costly catalyst reduction step as in WO 96/34896.